Conjugated polymers containing spirobifluorene units and the use thereof

ABSTRACT

The present invention relates to novel conjugated polymers comprising spirobifluorene units and their use in optoelectronic devices, preferably in, for example, displays based on polymeric organic light-emitting diodes.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 10/488,625, filed Sep. 10, 2004 now U.S. Pat. No. 7,323,533,which is a national stage application (under 35 U.S.C. § 371) of PCTApplication No. PCT/EP02/09628, filed Aug. 29, 2002, which claimsbenefit of German Application 101 43 353.0, filed Sep. 4, 2001.

The present patent application relates to novel conjugated polymers andtheir use in optoelectronic devices, preferably in, for example,displays based on polymeric organic light-emitting diodes.

Wide-ranging research on the commercialization of display and lightingelements based on polymeric (organic) light-emitting diodes (PLEDs) hasbeen carried on for about 10 years. This development was achieved by thefundamental developments disclosed in EP 423 283 (WO 90/13148). Incontrast to low molecular weight organic light-emitting diodes (OLEDs),which have already been introduced on the market, as demonstrated by thecommercially available car radios with an “organic display” fromPioneer, the PLEDs have still to be introduced on the market.Significant improvements are still necessary to make these displaysgenuinely competitive or superior to the liquid crystal displays (LCDs)which currently dominate the market.

EP-A-0 423 283, EP-A-0 443 861, WO 98/27136, EP-A-1 025 183 and WO99/24526 disclose polyarylene-vinylene derivatives as conjugatedpolymeric emitters.

EP-A-0 842 208, WO 99/54385, WO 00/22027, WO 00/22026 and WO 00/46321disclose polyfluorene derivatives as conjugated polymeric emitters.

EP-A-0 707 020 and EP-A-0 894 107 disclose polyspirobifluorenederivatives as conjugated polymeric emitters.

For the purposes of the present invention, conjugated polymers arepolymers which contain mainly sp²-hybridized carbon atoms, which mayalso be replaced by appropriate heteroatoms, in the main chain. This isequivalent to the alternating presence of double and single bonds in themain chain. “Mainly” means that naturally occurring defects which leadto interruptions to the conjugation do not invalidate the term“conjugated polymers”. However, the term does not include polymers whichcontain relatively large amounts of deliberately introducednonconjugated segments. Furthermore, for the purposes of the presenttext, the term conjugated is likewise used when, for example, arylamineunits and/or particular heterocycles (i.e. conjugation by N, O or Satoms) and/or organometallic complexes (i.e. conjugation via the metalatom) are present in the main chain. In contrast, units such as simple(thio)ether bridges, ester linkages, amide or imide linkages are clearlydefined as nonconjugated segments.

The general structure of PLEDs is disclosed in the abovementioned patentapplications or patents and is also described in more detail below.Further refinements (for example passive matrix addressing, activematrix addressing) are likewise known but are not of critical importancefor the further description of the present patent application.

At present, the commercialization of both single-color and multicolor orfull-color displays based on PLEDs is being evaluated. Whilesingle-color displays may be able to be produced by means of simplecoating technologies (e.g. doctor blade coating, spin coating),multicolor and full-color display elements will very probably requirethe use of printing processes (e.g. ink jet printing, offset printing,gravure printing processes, screen printing processes). However, allthese processes require soluble polymers.

Some of the conjugated polymers disclosed in the abovementioned patentapplications display good properties for the applications mentioned.Important properties include, in particular, the following:

-   -   High luminous efficiency and energy efficiency when used in        PLEDs.    -   Long operating life when used in PLEDs.    -   Low operating voltage,    -   Good storage stability, both when used in PLEDs and also before        introduction into corresponding devices.    -   Good solubility in organic solvents in order to make an        appropriate coating process possible at all.    -   Reasonable availability to make economical use in mass-produced        products possible.    -   Ability to achieve various colors to make full-color displays        possible.

It has now surprisingly been found that an improved, further-developednovel class of conjugated polymers has very good properties which aresuperior to the abovementioned prior art, These polymers and their usein PLEDs are subject matter of the present invention.

The invention provides conjugated polymers which comprise units of theformula (I)

together with one or more units selected from the following groups:

-   group 1: units which significantly increase the hole injection or    transport properties of the polymers;-   group 2: units which significantly increase the electron injection    or transport properties of the polymers,-   group 3: units which comprise combinations of individual units of    group 1 and group 2;-   group 4: units which alter the emission characteristics so that    phosphorescence can be obtained instead of fluorescence;    where the symbols and indices have the following meanings:-   X is identical or different on each occurrence and is in each case    CH, CR¹ or N,-   Z is identical or different on each occurrence and is in each case a    single chemical bond, a CR³R⁴ group, a —CR³R⁴—CR³R⁴— group, a    —CR³═CR⁴— group, O, S, N—R⁵, C═O, C═CR³R⁴ or SiR³R⁴;-   R¹ is identical or different on each occurrence and is in each case    a linear, branched or cyclic alkyl or alkoxy chain which has from 1    to 22 carbon atoms and in which one or more nonadjacent carbon atoms    may also be replaced by N—R⁵, O, S, —CO—O—, O—CO—O, where one or    more H atoms may also be replaced by fluorine, or is an aryl or    aryloxy group which has from 5 to 40 carbon atoms and in which one    or more carbon atoms may also be replaced by O, S or N, which may    also be substituted by one or more nonaromatic radicals R¹, or is    Cl, F, CN, N(R⁵)₂, N(R⁵)₃ ⁺, where two or more radicals R¹ may also    together form a ring system;-   R² is identical or different on each occurrence and is in each case    a linear, branched or cyclic alkyl or alkoxy chain which has from 1    to 22 carbon atoms and in which one or more nonadjacent carbon atoms    may also be replaced by N—R⁵, O, S, —CO—O—, O—CO—O, where one or    more H atoms may also be replaced by fluorine, or is an aryl or    aryloxy group which has from 5 to 40 carbon atoms and in which one    or more carbon atoms may also be replaced by O, S or N which may    also be substituted by one or more nonaromatic radicals R¹, or is    CN;-   R³, R⁴ are identical or different on each occurrence and are each H,    a linear, branched or cyclic alkyl chain which has from 1 to 22    carbon atoms and in which one or more nonadjacent carbon atoms may    also be replaced by N—R⁵, O, S, —CO—O—, O—CO—O, where one or more H    atoms may also be replaced by fluorine, or are each an aryl group    which has from 5 to 40 carbon atoms and in which one or more carbon    atoms may also be replaced by O, S or N, which may also be    substituted by one or more nonaromatic radicals R¹, or are each CN;    where a plurality of adjacent radicals R³ and/or R⁴ may together    also form a ring;-   R⁵ is identical or different on each occurrence and is in each case    H, a linear, branched or cyclic alkyl chain which has from 1 to 22    carbon atoms and in which one or more nonadjacent carbon atoms may    also be replaced by O, S, —CO—O—, O—CO—O, where one or more H atoms    may also be replaced by fluorine, or is an aryl group which has from    5 to 40 carbon atoms and in which one or more carbon atoms may also    be replaced by O, S or N, which may also be substituted by one or    more nonaromatic radicals R¹,-   m is identical or different on each occurrence and is in each case    0, 1, 2, or 3, preferably 0, 1 or 2, particularly preferably 0 or 1;-   n is identical or different on each occurrence and is in each case    0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 1 or    2;-   with the proviso that repeating units of the formula (I) and units    of groups 1 to 4 together make up at least 40%, preferably at least    60%, particularly preferably at least 80%, of all repeating units in    the polymer and that the ratio of repeating units of the formula (I)    to the sum of those of groups 1 to 4 is in the range from 20:1 to    1:2, preferably from 5:1 to 1:2, particularly preferably from 3:1 to    1:1.

Preferred units of group 1 are those of the formulae (II) to (XIX),

where the symbols R¹, R², R⁴, R⁵ and the indices n and m are as definedunder the formula (I) and

-   Ar¹, Ar², Ar³ are identical or different on each occurrence and are    aromatic or heteroaromatic hydrocarbons which have from 2 to 40    carbon atoms and may be substituted by one or more nonaromatic    radicals R¹; preferably substituted or unsubstituted aromatic    hydrocarbons having from 6 to 20 carbon atoms, very particularly    preferably appropriate benzene, naphthalene, anthracene, pyrene or    perylene derivatives;-   o is 1, 2 or 3, preferably 1 or 2.

Preferred units of group 2 are those of the formulae (XX) to (XXX)

where the symbols R¹ and indices m and n are as defined under theformula (I) and

-   p is 0, 1 or 2, preferably 0 or 1.

Preferred units of group 3 are those of the formulae (XXXI) to (XXXXVI),

where the symbols Ar¹, R¹, R², R³, R⁴, R⁵, Z and the indices m, n and pare as defined under the formula (I) and

-   o is 1, 2 or 3, preferably 1 or 2;-   p is 0, 1 or 2, preferably 0 or 1.

Preferred units of group 4 are those of the formulae (XXXXVII) to(XXXXX),

where the symbols R¹, R³ and the indices m and n are as defined underthe formula (I) and

-   M is Rh or Ir-   XX corresponds to the point of linkage in the polymer,-   YY is identical or different on each occurrence and is in each case    O, S or Se.

Preference is given to polymers according to the invention in whichstructural units of the formula (I) are present together with structuralunits of at least two of the groups 1 to 4.

Particular preference is in this case given to the simultaneous presenceof units of groups 1 and 2, or 1 and 3, or 1 and 4, or 2 and 3, or 2 and4, or 3 and 4.

Preference is also given to the simultaneous presence of structures fromgroups 1 and 2 and 3, or 1 and 2 and 4, or 2 and 3 and 4.

It is thus likewise particularly preferred for units of the formulae(II) to (V) and units of the formulae (XXIV) or (XXVI) to (XXX) to bepresent simultaneously.

Furthermore, it is likewise preferred for more than one structural unitfrom one group to be simultaneously present. Thus, preference is givento at least two structural units from group 1, or from group 2, or fromgroup 3, or from group 4 being present simultaneously.

Even when not indicated by the description, it may here be explicitlystated that the structural units of the formula (I) can beunsymmetrically substituted, i.e. different substituents R¹ and/or R²can be present on one unit, or these can also have different positionson each of the two sides.

The synthesis of the corresponding monomers is, for example, describedin detail in the abovementioned patent applications and patents.

Thus, for example, monomers which then give structures of the formula(I) in the polymer can be synthesized as described in EP-A-0676461,EP-A-0707020, EP-A-0894107 and the literature references cited therein.

The polymers of the invention are different from the previously knownpolyspirobifluorenes (as described in EP-A-0 707 020 and EP-A-0 894107): although these patent applications described polymers which cancomprise structures of the formula (I), no mention is made of theformulae (II) to (XXXXX). Although copolymers in which these are presentare disclosed, these copolymers comprise, according to the descriptions,mainly arylene or vinylene structures in addition to the structures ofthe formula (I). The presence of elements of the structures (II) to(XXXXX) brings the following surprising advantages:

-   (1) If structures of the formulae (II) to (XIX) are present,    improved charge injection and transport, especially for holes, is    observed. In use, this leads to a higher current and thus also a    higher luminance being achieved at a given voltage. This is of    critical importance especially for mobile applications (e.g.    displays for mobile telephones, PDAs, etc.), since the maximum    operating voltage is restricted here. For further details, see    Example P1 (comparison: C1-C3); also P2-P19, P21-P23, P25-P32,    P34-P41.-   (2) If structures of the formulae (XX) to (XXX) are present, an    analogous situation is observed for electrons. This can have    advantages similar to those described under (1). If both structures    of the formulae (II) to (XIX) and structures of the formulae (XX)    to (XXX) are present, this can further increase the effect. For    further details, see Examples P12-P24, P40, P41 (comparison: C1-C3).-   (3) Structures of the formulae (XXIX) to (XXXXV) make variation of    the electronic band gap possible, and thus allow alteration of the    color properties. While mainly blue emission is mentioned in the    abovementioned applications, the use of these structures makes it    possible to achieve blue-green, green, yellow, orange and red    emission as well. For further details, see P12-P35, P40, P41    (comparison: C1).-   (4) The structures of the formulae (XXXXVII) to (XXXXX) lead to a    different type of emission (known as phosphorescence) occurring.    This can give a higher quantum efficiency and thus also contribute    to an improvement in corresponding components.

The polymers of the invention generally have from 10 to 10 000,preferably from 50 to 5000, particularly preferably from 50 to 2000,repeating units.

The necessary solubility is ensured, in particular, by the substituentsR¹, R³ and/or R⁴. If substituents R² are present, these also contributeto the solubility.

To ensure sufficient solubility, it is necessary for on average at least2 nonaromatic carbon atoms per repeating unit to be present in thesubstituents. Preference is given to at least 4, particularly preferablyat least 8, carbon atoms. Some of these carbon atoms may also bereplaced by O or S. This can, however, mean that a certain proportion ofrepeating units, both of the formulae (I) to (XXXXX) and of otherstructural types, bear no further nonaromatic substituents.

To prevent morphology of the film being impaired, it is preferred thatthere are no long-chain substituents having more than 12 carbon atoms ina linear chain, preferably none having more than 8 carbon atoms,particularly preferably none having more than 6 carbon atoms.

Nonaromatic carbon atoms are, as in the description of, for example, R¹,present in appropriate linear, branched or cyclic alkyl or alkoxychains.

Preference is given to polymers according to the invention in whichX═C—H or C—R¹. Preference is also given to polymers according to theinvention in which the symbol Z represents a single chemical bond.

Furthermore, preference is given to polymers according to the inventionin which:

-   R¹ is identical or different on each occurrence and is in each case    a linear or branched alkyl or alkoxy chain having from 1 to 8 carbon    atoms, or is an aryl group having from 6 to 10 carbon atoms, which    are also substituted by one or more nonaromatic radicals R¹;-   n are identical or different and are each 1 or 2.

Furthermore, particular preference is given to polymers according to theinvention in which:

-   R¹ is identical or different on each occurrence and is in each case    a linear or branched alkyl or alkoxy chain having from 1 to 8 carbon    atoms, or is an aryl group having from 6 to 10 carbon atoms, which    are also substituted by one or more nonaromatic radicals R¹;-   n are identical or different and are each 1 or 2.

Furthermore, preference is given to polymers according to the inventionin which:

-   R² is identical or different on each occurrence and is in each case    a linear or branched alkyl or alkoxy chain having from 1 to 10    carbon atoms, where one or more H atoms may also be replaced by    fluorine, or is an aryl or aryloxy group having from 6 to 14 carbon    atoms, which may also be substituted by one or more nonaromatic    radicals R¹, or is CN;-   m is identical or different on each occurrence and is in each case 0    or 1.

Furthermore, particular preference is given to polymers according to theinvention in which:

-   R² is identical or different on each occurrence and is in each case    a linear or branched alkyl or alkoxy chain having from 1 to 8 carbon    atoms, where one or more H atoms may also be replaced by fluorine,    or is an aryl group having from 6 to 10 carbon atoms, which may also    be substituted by one or more nonaromatic radicals R¹;-   m is identical or different on each occurrence and is in each case 0    or 1, where m is equal to 0 for at least 50%, preferably at least    70%, very particularly preferably at least 90%, of all repeating    units of the formula (I) or (VI) to (XIII) present in the polymer.

Preference is also given to polymers according to the invention inwhich:

-   R³, R⁴ are identical or different on each occurrence and are each a    linear, branched or cyclic alkyl chain which has from 1 to 10 carbon    atoms and in which one or more nonadjacent carbon atoms may also be    replaced by O, where one or more H atoms may also be replaced by    fluorine, or are each an aryl group which has from 5 to 40 carbon    atoms and in which one or more carbon atoms may also be replaced by    O, S or N, which may also be substituted by one or more aromatic    radicals R¹.

The polymers of the invention are per se copolymers which have at leasttwo different repeating units (one of the formula (I), one selected fromamong the formulae (II) to (XXXXX). The copolymers of the invention canhave random, alternating or block structures, or have a plurality ofthese structures present in an alternating fashion.

However, preference is also given to copolymers according to theinvention which have one or more different structures of the formula (I)and/or one or more different structures of the formulae (II) to (XXXXX).

The use of a plurality of different structural elements enablesproperties such as solubility, solid-state morphology, color, chargeinjection and transport properties, thermal stability, electroopticalcharacteristics, etc., to be adjusted.

Preferred polymers according to the invention are polymers in which atleast one structural element has charge transport properties.

For the purposes of the present patent application, such structuralelements are as follows: if HOMOPOLYMERS or OLIGOMERS were produced fromthese structural elements, they would have a higher charge carriermobility, at least for one charge carrier, i.e. either electrons orholes, as is the case for a polymer consisting exclusively of structuralelements of the formula (I). The charge carrier mobility (measured incm²/(V*s)) is preferably at least a factor of 10 higher, particularlypreferably a factor of at least 50 higher.

Structural elements which have hole transport properties are, forexample, triarylamine derivatives, benzidine derivatives,tetraarylene-para-phenylenediamine derivatives, phenothiazinederivatives, phenoxazine derivatives, dihydrophenazine derivatives,thianthrene derivatives, benzo-p-dioxin derivatives, phenoxathiinederivatives, carbazole derivatives, azulene derivatives, thiophenederivatives, pyrrole derivatives, furan derivatives and further O, S orN-containing heterocycles having a high HOMO (HOMO=highest occupiedmolecular orbital); these heterocycles preferably lead to an HOMO in thepolymer of less than 5.8 eV (relative to vacuum level), particularlypreferably less than 5.5 eV.

Preference is given to polymers according to the invention which furthercomprise at least one structural unit of the formulae (II) to (XXX). Theproportion of these structural elements is at least 1%, preferably atleast 5%. The maximum proportion is 50%, preferably 30%. Thesestructural units, too, can be incorporated randomly, in an alternatingfashion or as blocks in the polymer.

The way in which the structures are incorporated has already beenindicated directly for many of them (cf., for example, formulae (II) to(V) and formulae (XIII) to (XIX)). In the case of other structures, anumber of possibilities are in each case possible according to theinvention. However, in these cases there are also preferred ways inwhich they can be incorporated:

In the case of the N-containing tricyclic heterocycles (formula (VI) toformula (VIII)), linkage via carbon atoms in the para position relativeto the nitrogen (i.e. in the case of phenothiazine and phenoxazinederivatives: 3,7 positions; in the case of dihydrophenazine derivatives.2,7 or 3,7 positions) is preferred in each case. An analogous situationapplies to carbazole derivatives (formula (XII)). On the other hand, inthe case of the O- and/or S-containing tricycles (formulae (IX) to(XI)), both ortho and para positions relative to one of the heteroatomsare preferred. In the case of heterocycles in which more than the ringis present, linkage to the polymer via only one ring or via two rings ispossible.

Monomers for the incorporation of structural units of formula (II),formula (III), formula (IV) and formula (V) can be synthesized, forexample, as described in WO98/06773.

Monomers for the incorporation of structural units of formula (VI),formula (VII) and formula (VIII) can be synthesized, for example, asdescribed by M. Jovanovic et al., J. Org. Chem. 1984, 49, 1905, and H.J. Shine et al., J. Org. Chem. 1979, 44, 3310. Monomers for theincorporation of structural units of formula (IX) and formula (X) can besynthesized, for example, as described in J. Lovell et al., Tetrahedron1996, 52, 4745, U.S. Pat. No. 4,505,841 and the references citedtherein.

Monomers for the incorporation of structural units of formula (XI) canbe synthesized, for example, as described by A. D. Kuntsevich et al.,Zh. Obshch. Khim. 1994, 64, 1722, and A. D. Kuntsevich et al., Dokl.Akad. Nauk 1993, 332, 461. Many halogenated monomers for theincorporation of structural units of the formula (XII) are known fromthe literature and some of them are even commercially available. Alisting of all possible methods would go beyond the scope of the presentpatent application.

Monomers for the incorporation of structural units of the formula (XIII)can, for example, be synthesized as described by R. H. Mitchell et al.,Org. Prep. Proced. Int. 1997, 29, 715.

Many halogenated monomers for the incorporation of structural units ofthe formula (XIV) are known from the literature and some of them areeven commercially available. A listing of all possible methods would gobeyond the scope of the present patent application.

Monomers for the incorporation of structural units of the formula (XV)can be synthesized, for example, as described by H. M. Gilow et al., J.Org. Chem. 1981, 46, 2221, and G. A. Cordell, J. Org. Chem. 1975, 40,3161.

Monomers for the incorporation of structural units of the formula (XVI)can be synthesized, for example, as described by M. A. Keegstra et al.,Synth. Commun. 1990, 20, 3371, and R. Sornay et al., Bull. Soc. Chim.Fr. 1971, 3, 990, and some of them are also commercially available.

Some monomers for the incorporation of structural units of the formula(XVII) are commercially available.

Monomers for the incorporation of structural units of the formula(XVIII) can be synthesized, for example, as described in JP 63-250385.

Monomers for the incorporation of structural units of the formula (XIX)can be synthesized, for example, as described by M. El Borai et al.,Pol. J. Chem. 1981, 55, 1659, and some of them are also commerciallyavailable.

The literature references listed here for the synthesis of monomerswhich in the polymer give structures of the formulae (II) to (XIX)describe mainly the synthesis of halogen derivatives, preferably brominederivatives. From these, a person skilled in the art can easily prepare,for example, boronic acid derivatives or stannates. This can beachieved, for example, by metallation (e.g. by means of Mg (Grignardreaction) or Li (e.g. by means of Bu—Li)) and subsequent reaction withappropriate boron or tin derivatives, e.g. trialkyl borates ortrialkyltin halides. It is, however, naturally also possible to produceboronic acid derivatives from the corresponding bromides in the presenceof transition metal catalysts using boranes or diboranes. There is agreat variety of further methods known from the literature and these cannaturally also be used by a person skilled in the art.

Structural elements of group 2 are, for example, pyridine derivatives,pyrimidine derivatives, pyridazine derivatives, pyrazine derivatives,oxadiazole derivatives, quinoline derivatives, quinoxaline derivatives,phenazine derivatives and further O-, S- or N-containing heterocycleshaving a low LUMO (LUMO=lowest unoccupied molecular orbital); theseheterocycles preferably lead to an LUMO in the polymer of more than 2.7eV (relative to vacuum level), particularly preferably more than 3.0 eV.

Preference is given to polymers according to the invention which containat least one structural unit of the formulae (XX) to (XXX). Theproportion of these structural elements is at least one 1%, preferablyat least 5%. The maximum proportion is 70%, preferably 50%. Thesestructural units, too, can be incorporated randomly, in an alternatingfashion or in blocks in the polymer.

The way in which the structures are incorporated has already beenindicated directly for many of them (cf., for example, formulae (XXIV),(XXIX) und (XXX)). In the case of other structures, a number ofpossibilities are in each case possible according to the invention.However, in these cases there are also preferred ways in which they canbe incorporated:

In the case of pyridine derivatives, linkage via the 2,5 or 2,6positions is preferred, in the case of pyrazine and pyrimidinederivatives that via the 2,5 positions is preferred and in the case ofpyridazine derivatives that via the 3,6 positions is preferred. In thecase of the bicyclic heterocycles, a plurality of linkages are generallypossible and also preferred. However, in the case of quinoxaline,linkage via the 5,8 positions is unambiguously preferred.

In the case of phenazine, it may, as indicated, be preferred thatlinkage occurs via the two outer rings or that incorporation is via onlyone ring. Preferred positions are therefore incorporation at carbonatoms 1,4 or 2,3 or 2,7 or 3,7.

The chemistry of pyridine derivatives (XX) has been examined in greatdetail. Thus, the preparation of 2,5- and 2,6-dihalopyridines islikewise known. Reference may here be made to the numerous standardworks on heterocyclic chemistry. Furthermore, many of the compounds arealso commercially available. Monomers for the incorporation ofstructural units of the formula (XXI) can be synthesized, for example,as described in Arantz et al., J. Chem. Soc. C 1971, 1889. Monomers forthe incorporation of structural units of the formula (XXII) can besynthesized, for example, as described in Pedrali et al., J. Org. Synth.1958, 23, 778.

Monomers for the incorporation of structural units of the formula(XXIII) can be synthesized, for example, as described by Ellingson etal., J. Am. Chem. Soc. 1949, 71, 2798.

Monomers for the incorporation of structural units of the formula (XXIV)can be synthesized, for example, as described in Stolle et al., J.Prakt. Chem. 1904, 69, 480.

Monomers for the incorporation of structural units of the formula (XXV)can be synthesized, for example, as described in Metzger, Chem. Ber.1884, 17, 187, and A. I. Tochilkin et al., Chem. Heterocycl. Compd.(Engl. Transl) 1988, 892. Monomers for the incorporation of structuralunits of the formula (XXVI) can be synthesized, for example, asdescribed in Calhane et al., J. Am. Chem. Soc. 1899, 22, 457, and T.Yamamoto et al., J. Am. Chem. Soc. 1996, 118, 3930. Monomers for theincorporation of structural units of the formulae (XXVII) and (XXVIII)can be synthesized, for example, as described in L. Horner et al., J.Liebigs Ann. Chem., 1955, 597, 1, and P. R. Buckland et al., J. Chem.Res. Miniprint 1981, 12, 4201.

Monomers for the incorporation of structural units of the formula (XXIX)can be synthesized, for example, as described in K. Pilgram et al., J.Heterocycl. Chem. 1970, 7, 629, and WO 00/55927.

Monomers for the incorporation of structural units of the formula (XXX)can be synthesized, for example, as described in Hammick et al., J.Chem. Soc. 1931, 3308, and K. Pilgram et al., J. Heterocyl. Chem. 1974,11, 813.

The references cited here for the synthesis of monomers which in thepolymer gives structures of the formulae (XX) to (XXX) also describemainly the synthesis of halogen derivatives, preferably brominederivatives. Using these as a starting point, a person skilled in theart can, as also described above for the properties which increase holemobility, carry out further transformations, e.g. to give boronic acidderivatives or stannates.

Furthermore, preference is also given to polymers according to theinvention in which units of group 3 are present.

Particular preference is accordingly given to polymers according to theinvention which comprise both one or more structures of the formulae(II) to (XIX) and one or more structures of the formulae (XX) to (XXX).

The abovementioned limits for the respective proportion continue toapply here. It can be very particularly preferred for the polymers ofthe invention to comprise units in which structures which increase holemobility and electron mobility follow one another directly or alternate,as is the case, for example, for the formulae (XXXI) to (XXXXV) and isindicated somewhat more generally for the formula (XXXXVI). Monomers ofthe formulae (XXXI) to (XXXXVI) can be synthesized by the methodsindicated for the formulae (III) to (XXX) by appropriate combination ofthe appropriate precursors. It may also be pointed out that at leastsome examples of syntheses are given in the abovementioned patentapplications WO 00/46321 and WO 00/55927. Such structures are alsoreported in, for example, in H. A. M. Mullekom et al., Chem. Eur. J.,1998, 4, 1235. It may be pointed out that the structures of the formulae(XXXI) to (XXXXVI) do not in any way restrict the invention thereto, butit is naturally simple for a person skilled in the art to synthesizesuitable combinations of the abovementioned structures (III) to (XIX) or(XX) to (XXX) and to incorporate these into the polymers of theinvention.

Preference is also given to copolymers whose emission characteristicshave been altered so that phosphorescence takes place instead offluorescence. This is, in particular, the case when organometalliccomplexes have been incorporated in the main chain. Particularpreference is in this case given to complexes of the d series transitionmetals, very particularly preferably those of the higher metals of theiron, cobalt and nickel triads, i.e. complexes of ruthenium, osmium,rhodium, iridium, palladium and platinum. Such complexes are frequentlyable to emit light from excited triplet states, which frequentlyincreases the energy efficiency. The use of such complexes in lowmolecular weight OLEDs is described, for example, in M. A. Baldo, S.Lamansky, P. E. Burrows, M. E. Thompson, S. R. Forrest, Applied PhysicsLetters, 1999, 75, 4-6. Nothing has yet been reported about theincorporation of these compounds in polymers. Corresponding monomers aredescribed in the as yet unpublished patent application DE 10109027.7.Such structural elements can also have a substantial influence on theemission color and the energy efficiency of the resulting polymers.

Examples for particularly preferred complexes which can be incorporatedinto the polymers of the invention are the abovementioned compounds ofthe formulae (XXXXVII) to (XXXXX).

The preparation of corresponding monomers is described in theabove-mentioned unpublished patent application DE 10109027.7, which ishereby incorporated by reference into this disclosure of the presentinvention.

Preferred copolymers which further comprise additional structuralelements in addition to those of the formula (I) and the formulae (II)to (XXXXX) also include ones which comprise at least one furtheraromatic structure or another conjugated structure which does not comeunder one of the abovementioned groups, i.e. has little if any influenceon the charge carrier mobilities or is not an organometallic complex.Such structural elements can influence the morphology and also theemission color of the resulting polymers.

Preference is given to aromatic structures which have from 6 to 40carbon atoms or stilbene or bisstyrylarylene derivatives which may eachbe substituted by one or more nonaromatic radicals R¹.

Particular preference is given to the incorporation of 1,4-phenylene,1,4-naphthylene, 1,4- or 9,10-anthracenylene, 1,6- or 2,7- or4,9-pyrene, 3,9- or 3,10-perylene, 2,7- or 3,6-phenanthrene,4,4′-biphenylene, 4,4″-terphenylene, 4,4′-bi-1,1′-naphthylene,4,4′-stilbene or 4,4″-bisstyrylarylene derivatives.

These structures are also mentioned in the patent applications EP-A-0707 020 and EP-A-0 894 107 cited at the outset, but in contrast to theinformation given there, these are introduced into the present novelpolymers only as additional possibilities for obtaining furthermodifications.

Such structures are widely known in the literature and most are alsocommercially available. A listing of all possible synthetic variantswould go far beyond the scope of the present patent application.

The polymers of the invention are generally prepared by polymerizationof two or more monomers of which at least one subsequently givesstructures of the formula (I) and at least one more gives structuresselected from among the formulae (II) to (XXXXX).

There are in principle a relatively large number of differentpolymerization reactions which can be used, but the types listed belowhave been found to be particularly useful. In principle, all thesereaction types give C—C linkages:

-   (A) Polymerization by the SUZUKI method: Here, monomers used are,    firstly, bishalides and, secondly, bisboronic acids and    corresponding derivatives, or corresponding monohalide-monoboronic    acid derivatives, and these are coupled in the presence of palladium    catalysts and solvents under basic conditions. Reactions of this    type which lead to conjugated polymers have been described many    times. There is a series of proposals for making such reactions    proceed efficiently and lead to high molecular weight polymers;    these are described, inter alia, in the following references: (i) EP    707.020, (ii) EP 842.208, (iii) EP 1.025.142, (iv) WO 00/53656    and (v) in the references cited therein. The corresponding    descriptions are hereby incorporated by reference into the    disclosure of the present patent application.-   (B) Polymerizations by the YAMAMOTO method: Here, exclusively    bishalides are used as monomers. The polymerizations are carried out    in the presence of solvents, a nickel compound, possibly a base and,    if desired, a reducing agent and also further ligands. Reactions of    this type which lead to conjugated polymers have been described    relatively often. There are some proposals for making such reactions    proceed efficiently and lead to high molecular weight polymers;    these are described, inter alia, in the following references: (i) M.    Ueda et al., Macromolecules, 1991, 24, 2694, (ii) T. Yamamoto et    al., Macromolecules 1992, 25, 1214, (iii) T. Yamamoto et al., Synth.    Met. 1995, 69, 529-31, (iv) T. Yamamoto et al., J. Organometallic    Chem. 1992, 428, 223, (v) I. Colon et al., J. Poly. Sci.: Part A:    Poly. Chem. 1990, 28, 367, (vi) T. Yamamoto et al., Macromol. Chem.    Phys. 1997, 198, 341. The corresponding descriptions are hereby    incorporated by reference into the disclosure of the present patent    application.-   (C) Polymerizations by the STILLE method: Monomers used here are,    firstly, bishalides and, secondly, bisstannanes, or corresponding    monohalide-monostannanes, and these are coupled in the presence of    palladium catalysts and solvents, possibly under basic conditions.    Reactions of this type which lead to conjugated polymers have been    described in the literature. However, they have not been examined to    the same extent as the SUZUKI or YAMAMOTO coupling. A conjugated    polymer obtained by STILLE coupling is described, for example, in W.    Schorf et al., J. Opt. Soc. Am. B 1998, 15, 889. A review of the    possibilities and the difficulties of the STILLE reaction is given,    inter alia, in V. Farina, V. Krishnamurthy, W. J. Scott (editors)    “The Stille Reaction” 1998, Wiley, New York, N.Y. The corresponding    descriptions are hereby incorporated by reference into the    disclosure of the present patent application.

After the polymerization (polycondensation) has been carried out, thepolymers synthesized firstly have to be separated off from the reactionmedium. This is generally achieved by precipitation in a nonsolvent. Thepolymers obtained subsequently have to be purified, since especially thecontent of low molecular weight organic impurities and also the ioncontent or content of other inorganic impurities sometimes have verystrong effects on the use properties of the polymers in PLEDs. Thus, lowmolecular weight constituents can considerably reduce the efficiency andalso cause a dramatic deterioration in the operating life. The presenceof inorganic impurities has an analogous effect.

Suitable purification methods include, firstly, precipitation proceduresin which the polymer is repeatedly dissolved and precipitated in anonsolvent. It is advantageous to pass the polymer solution through afilter in order to separate off undissolved constituents (get particles)and also dust particles. A further possibility is the use of ionexchangers to lower the content of ions. Stirring a polymer solutionwith an aqueous solution containing, for example, chelating ligands, canalso be helpful. Further organic or inorganic extraction processes, e.g.with solvent/nonsolvent mixtures, or using supercritical CO₂ can alsoresult in considerable improvements here.

The novel polymers obtained in this way can then be used in PLEDs. Thisis usually done using the following general method, which then naturallyhas to be adapted appropriately to the specific case:

-   -   A substrate (e.g. glass or a plastic such as specially treated        PET) is coated with a transparent anode material (for example        indium-tin oxide, ITO); the anode is subsequently structured        (e.g. photolithographically) and connected according to the        desired application. It is also possible for the entire        substrate and the appropriate circuitry firstly to be produced        by a quite complicated process to make active matrix control        possible.    -   After this, a conductive polymer, e.g. a doped polythiophene or        polyaniline derivative, is generally firstly applied either over        the entire area or only to the active (=anodic) places. This is        generally carried out by coating methods in which a dispersion        of the appropriate polymer is applied. This can in principle be        carried out using the methods described below for the        light-emitting polymer. The thickness of this polymer layer can        vary within a wide range, but for practical use will be in the        range from 10 to 1000 nm, preferably from 20 to 500 nm.    -   A solution of a polymer according to the invention is then        applied, depending on the intended use. For multicolor or        full-color displays, a plurality of different solutions are then        applied in various regions to produce appropriate colors. The        polymers of the invention are for this purpose firstly dissolved        individually (it can also be advisable to use blends of two or        more polymers) in a solvent or solvent mixture, possibly        mechanically after-treated and subsequently filtered. Since the        organic polymers and especially the interfaces in the PLED are        sometimes extremely sensitive to oxygen or other constituents of        the air, it is advisable to carry out this operation under        protective gas. Suitable solvents include aromatic liquids such        as toluene, xylenes, anisole, chlorobenzene, and also others        such as cyclic ethers (e.g. dioxane, methyldioxane) or amides,        for example NMP or DMF, and also solvent mixtures, as are        described in the unpublished patent application DE 101111633.0.    -   The above-described supports can then be coated with the        solutions, either over their entire area, e.g. by spin coating        or doctor blade techniques, or else in a resolved manner by        means of printing processes such as ink jet printing, offset        printing, screen printing processes, gravure printing processes,        and the like. These abovementioned solutions are novel and are        thus likewise subject matter of the present invention.    -   If desired, electron injection materials can then be applied to        these polymer layers, e.g. by vapor deposition or from solution        using methods as have been described for the emitting polymers.        As electron injection materials, it is possible to use, for        example, low molecular weight compounds such as triarylborane        compounds or aluminum trishydroxyquinolinate (Alq₃) or        appropriate polymers such as polypyridine derivatives and the        like. It is also possible to convert thin layers of the emitting        polymers into electron injection layers by appropriate doping.    -   A cathode is subsequently applied by vapor deposition. This is        generally carried out by means of a vacuum process and can, for        example, be achieved either by thermal vapor deposition or by        plasma spraying (sputtering). The cathode can be applied over        the entire area or in a structured fashion by means of a mask.        As cathode, use is generally made of metals having a low work        function, e.g. alkali metals, alkaline earth metals and f series        transition metals, e.g. Li, Ca, Mg, Sr, Ba, Yb, Sm, or else        aluminum or alloys of metals, or multilayer structures        comprising various metals. In the latter case, metals having a        relatively high work function, e.g. Ag, tan be concomitantly        used. It can also be preferred to introduce a very thin        dielectric layer (e.g. LiF or the like) between the metal and        the emitting polymer or the electron injection layer. The        cathodes generally have a thickness of from 10 to 10 000 nm,        preferably from 20 to 1000 nm.    -   The PLEDs or displays produced in this way are subsequently        provided with appropriate electrical connections and        encapsulated, and then tested or used.

As described above, the polymers of the invention are especially usefulas electroluminescence materials in the PLEDs or displays produced inthe manner described.

For the purposes of the invention, electroluminescence materials arematerials which can be used as active layer in a PLED. Active layermeans, in the present context, that the layer is capable of emittinglight (light-emitting layer) on application of an electric field and/orthat it improves the injection and/or transport of the positive and/ornegative charges (charge injection layer or charge transport layer).

The invention therefore also provides for the use of a polymer accordingto the invention in a PLED, in particular as electroluminescencematerial.

The invention thus likewise provides a PLED having one or more activelayers of which at least one comprises one or more polymers according tothe invention. The active layer can, for example, be a light-emittinglayer and/or a transport layer and/or a charge injection layer.

PLEDs are employed, for example, as self-illuminating display elementssuch as control lamps, alphanumeric displays, multicolor or full-colordisplays, information signs and in optoelectronic couplers.

The present description and the examples below describe the use ofpolymers according to the invention or blends of polymers according tothe invention in PLEDs and the corresponding displays. Despite thisrestriction of the description, a person skilled in the art will easilybe able, without making a further inventive step, to utilize thepolymers of the invention for further applications in other electronicdevices, e.g. for organic integrated circuits (O-ICs), in organic fieldeffect transistors (OFETs), in organic thin film transistors (OTFTs),for organic solar cells (O-SCs) or organic laser diodes (O-lasers), toname only a few applications.

The present invention is illustrated by the following examples withoutbeing restricted thereto. A person skilled in the art will be able, onthe basis of the description and the examples provided, to preparefurther solutions according to the invention and employ these forproduction layers without having to make an inventive step.

Part A: Synthesis of the Monomers:

A1: Monomers for Units of the Formula (I) (Spiro Compounds)

A1.1. Preparation of Symmetrical Spiro Monomers

Preparation of 2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1) and the ethyleneglycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2) Preparation of 2,7-dibrom-2′,7′-di-tert-butylspirobifluorene(S-SY3) Preparation of the glycol ester of2′,7′-di-t-butylspirobifluorene-2,7-bisboronic acid (S-SY4)

The Synthesis is Described in the Unpublished German patent applicationDE 10114477.6.

A1.2. Preparation of Unsymmetrical Spiro Monomers

The preparation of the unsymmetrical spirobifluorene monomers wascarried out according to the following scheme:

The synthesis will be described in detail for the monomer S-US1; thefurther monomers were prepared by an analogous method.

Preparation of2,7-dibromo-8′-t-butyl-5′-(4″-t-butylphenyl)-2′,3′-bis(2-methylbutyloxy)spirobifluorene(S-US1) Preparation of5′-t-butyl-2′-(4″-t-butylphenyl)-2,3-bis(2-methylbutyloxy)biphenyl

205.5 g (0.595 mol) of 2-bromo-4,4′-di-t-butylbiphenyl, 188.7 g (0.641mol) of 3,4-bis(2-methylbutyloxy)benzeneboronic acid and 177.2 g (1.282mol) of K₂CO₃ were suspended in 840 ml of toluene and 840 ml of H₂O andthe mixture was saturated with N₂ for 1 hour. 1.48 g (1.28 mmol) ofPd(PPh₃)₄ were subsequently added under protective gas and the mixturewas stirred vigorously under reflux for about 8 hours under a blanket ofprotective gas. 630 ml of 1% strength NaCN solution were added and themixture was stirred for 2 hours.

The organic phase washed three times with water, dried over Na₂SO₄,filtered and subsequently evaporated completely on a rotary evaporator.

This gave 300.2 g (98%) of a light-brown oil which, according to ¹H NMR,had a purity of 97% and was used directly in the subsequent reaction.

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.5-7.3 (m, 3H); 7.23 (m, 2H); 7.08 (m,2H); 6.81-6.87 (m, 2H); 6.51 (d, 1H); 3.87-3.7 (m, 2H, OCH₂); 3.44-3.30(m, 2H, OCH₂); 1.88 (m, 1H, H—C); 1.71 (m, 1H, H—C); 1.62-1.42 (m, 2H,CH₂); 1.39 (s, 9H, C(CH₃)₃); 1.29 (s, 9H, C(CH₃)₃); 1.10-1.33 (m, 4H,CH₂); 1.07-0.83 (m, 12H, 4×CH₃).

Preparation of2-bromo-5′-t-butyl-2′-(4″-t-butylphenyl)-4,5-bis(2-methylbutyloxy)biphenyl

300.2 g (0.583 mol) of5′-t-butyl-2′-(4″-t-butylphenyl)-2,3-bis(2-methylbutyloxy)biphenyl weredissolved in 500 ml of ethyl acetate under protective gas and cooled to0° C. 103.8 g (0.583 mol) of N-bromosuccinimide were then added as asolid and the mixture was warmed to room temperature. The reaction wascomplete after 1 hour. The organic phase washed three times with water,dried, evaporated on a rotary evaporator and subsequently recrystallizedfrom ethanol. This gave 294.1 g (85%) of a colorless solid which had apurity of >99% according to ¹H-NMR and of 99.7% according to HPLC.

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.45-7.35 (m, 3H); 7.19 (m, 2H); 7.06 (m,3H); 6.50 (d, 1H); 3.87-3.70 (m, 2H, OCH₂); 3.55-3.25 (m, 2H, OCH₂);1.88 (m, 1H, H—C); 1.67 (m, 1H, H—C); 1.62-1.42 (m, 1H, CH₂); 1.38 (s+m,10H, C(CH₃)₃+1H); 1.27 (s+m, 10H, C(CH₃)₃+1H); 1.15 (m, 1H, CH₂); 1.12(d, 3H, CH₃); 0.95 (t, 3H, CO₃); 0.9-0.8 (m, 6H, 2×CH₃).

Preparation of2,7-dibromo-8′-t-butyl-5′-(4″-t-butylphenyl)-2′,3′-bis(2-methylbutyloxy)spirobifluorene(S-US1)

294 g (0.495 mol) of2-bromo-5′-t-butyl-2′-(4″-t-butylphenyl)-4,5-bis(2-methylbutyloxy)biphenylwere dissolved in 700 ml of distilled THF. 12.4 g (0.510 mol) ofmagnesium turnings and a few crystals of iodine were placed in a flaskkept under protective gas. The mixture was heated briefly and 10% of theamount of starting material in THF was added. After the reaction hadstarted, the remainder was added at such a rate that the reactionmixture refluxed without further introduction of heat (one hour). Themixture was refluxed for a further 3 hours and a further 100 ml ofdistilled THF were then added. A suspension of 189.7 g (561.2 mmol) of2,7-dibromfluoren-9-one in 500 ml of distilled THF was cooled to 0° C.The Grignard solution was then added dropwise to the suspension at atemperature of 0-5° C. The mixture was subsequently refluxed for 90minutes. After cooling to room temperature, the reaction mixture wasadmixed with a mixture of 600 ml of ice water, 33.2 ml of HCl and 900 mlof ethyl acetate and the organic phase washed twice with NaHCO₃ solutionand water, subsequently dried and evaporated on a rotary evaporator.This light-brown oil was heated to boiling with 3000 ml of glacialacetic acid and 21 ml of 37% hydrochloric acid under protective gas,resulting in precipitation of a colorless solid. The mixture was heatedfor another 2 hours, cooled to RT, the solid was filtered off withsuction and washed with 1500 ml of glacial acetic acid. A singlerecrystallization from 2-butanone gave 310.1 g (75%) of the product,which had a purity of >99.5% according to ¹H-NMR and of 99.8% accordingto HPLC.

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.67 (d, 2H); 7.55 (d, 2H); 7.53-7.43 (m,5H); 7.26 (d, 1H); 6.97 (s, 1H); 6.27 (s, 1H); 5.60 (s, 1H), 3.40-3.21(m, 4H, OCH₂); 1.67-1.55 (m, 2H, H—C); 1.42 (s+m, 11H, C(CH₃)₃+2H);1.19-1-01 (m, 2H); 1.27 (s+m, 10H, C(CH₃)₃+1H); 1.15 (m, 1H, CH₂); 1.12(d, 3H, CH₃); 0.95 (t, 3H, CH₃); 0.82 (s+m, 21H, 1×C(CH₃)₃+4×CH₃).

The further monomers are summarized in the following table:

Total yield Purity at the end according to Starting aryl of the aboveHPLC Monomer bromide scheme [%] [%] S-US1

62.5 99.8 S-US2

60.3 99.6 S-US3

27.8 99.8 (as a mixture of 2 isomers in a ratio of about 70/30) S-US4

44.2 99.3

To give an overview, the monomers of the formula (I) whose preparationis carried out here are summarized below:

A2: Monomers for Units of the Formulae (II) to (V) (Triarylamines,Phenylenediamine Derivatives and Tetraarylbenzidines)

Preparation ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1)Preparation ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-methoxyphenyl)benzidine (AM2)Preparation of 4,4′-dibromotriphenylamine (AM3)

The synthesis is described in the unpublished German patent applicationDE 10114477.6.

To give an overview, the monomers of the formulae (II) to (V) whosepreparation is carried out here are summarized below:

A3: Monomers for Units of the Formula (XXVI)

The preparation of substituted quinoxaline monomers was carried outaccording to the following scheme:

Preparation of 5,8-dibromodiphenylquinoxaline (CH-b)

A solution of 5.3 g (20 mmol) of 3,6-dibromo-1,2-phenylenediamine 1,4 g(19 mmol) of benzil 2b, 4.2 g of sodium acetate and 150 ml of glacialacetic acid were refluxed for 4 hours. The precipitate was filtered off,washed with 100 ml of water and recrystallized twice from dioxane.Drying under reduced pressure at 50° C. gave the pure product in theform of colorless crystals, which according to HPLC had a purity ofabout 99.5%. The yield was 6.45 g (73%).

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.92 (s, 2H), 7.67 (d, ³J_(HH)=1.67 Hz,2H), 6.66 (d, ³J_(HH)=1.67 Hz, 2H), 7.37 (m, 6H).

The other quinoxaline monomers CH-a and CH-c to CH-m were prepared in ananalogous manner. The individual quinoxaline monomers are indicated inthe scheme above.

A4: Monomers for Units of the Formulae (XXIX) and (XXX)

Preparation of 4,7-dibromobenzo[1,2,5]thiadiazole (N2S-1) Preparation of4,7-dibromobenzofurazone (N2O-1)

The synthesis described in the unpublished German application DE10114477.6.

To give a better overview, the monomers described, of the formulae(XXIX) and (XXX), are depicted below.

A5: Monomers for Units of the Formulae (XXXI) to (XXXXVI)

Such monomers were prepared according to the following scheme:

Preparation of bis-4,7-(2′-bromo-5′-thienyl)-2,1,3-benzothiadiazole(N2S-1)-T2-Br2

Preparation of bis-4,7-(thien-2-yl)-2,1,3-benzothiadiazole 13.5 g (11.7mmol, 0.065 eq.) of Pd(PPh₃)₄ were added to a nitrogen-saturated mixtureconsisting of 52.92 g (180 mmol) of1′,4′-dibromo-2,1,3-benzothiadiazole, 60 g (468.9 mmol, 2.6 eq.) ofthiophene-2-boronic acid, 149 g (702 mmol, 3.9 eq.) of K₃PO₄, 1 l ofdioxane and 1 l of water and the suspension was heated at 80° C. for 7hours. 0.8 g of NaCN was then added and the aqueous phase was separatedoff. The organic phase washed twice with H₂O and subsequently dried overNa₂SO₄. The solvent was removed and the residue was recrystallized twicefrom CH₂Cl₂/MeOH to give dark red needles which according to HPLC had apurity of about 99%. The yield was 43 g (80%).

¹H NMR (CDCl₃, 500 MHz): [ppm]=8.11 (dd, ³J_(HH)=3.68 Hz, 2H), 7.89 (s,2H), 7.46 (dd, ³J_(HH)=5.2 Hz, 2H), 7.21 (dd, ³J_(HH)=5.2 Hz, 2H).

Preparation of bis-4,7-(2′-bromo-5′-thienyl)-2,1,3-benzothiadiazole(N2S-1)-T2-Br2

9.51 g (54 mmol) of N-bromosuccinimide were added to a solution of 7.72g (25.7 mmol) of bis-4,7-(thien-2-yl)-2,1,3-benzothiadiazoline in 770 mlof chloroform over a period of 15 minutes at RT in a protective gasatmosphere and with exclusion of light. The mixture was stirred for 6hours, and 80 ml of saturated Na₂CO₃ solution were subsequently added,the organic phase was separated off and dried over Na₂SO₄. After removalof the solvent, the residue was recrystallized from DMF/EtOH. Dying at50° C. under reduced pressure gave the product in the form ofyellow-orange crystals which according to HPLC had a purity of about99.6%. The yield was 10 g (85%).

¹H NMR (DMSO-d₆, 500 MHz): [ppm]=8.17 (s, 2H), 7.95 (d, ³J_(HH)=4.2 Hz,2H), 7.40 (d, ³J_(HH)=4.2 Hz, 2H).

The compounds (CH-a to CH-m, 5, 6)-T2-Br2 could be prepared analogously.

Preparation of 4-bromo-7-(2′-bromo-5′-thienyl)-2,1,3-benzothiadiazole(N2S-1)-T1-Br2 Preparation of4-bromo-7-(thien-2-yl)-2,1,3-benzothiadiazole

6.75 g (5.85 mmol, 0.032 eq.) of Pd(PPh₃)₄ were added to anitrogen-saturated mixture consisting of 52.92 g (180 mmol) of1′,4′-dibromo-2,1,3-benzothiadiazole, 30 g (234.4 mmol, 1.3 eq.) ofthiophene-2-boronic acid, 74.5 g (351 mmol, 1.95 eq.) of K₃PO₄, 2 l ofdioxane and 2 l of water and the suspension was heated at 80° C. forseven hours. 0.8 g of NaCN were then added and the aqueous phase wasseparated off. The organic phase washed twice with H₂O and subsequentlydried over Na₂SO₄. The solvent was removed and the residue wasrecrystallized twice from CH₂Cl₂/MeOH to give dark red needles whichaccording to HPLC had a purity of about 99%. The yield was 30 g (60%).

¹H NMR (CDCl₃, 500 MHz): [ppm]=8.01 (d, ³J_(HH)=3.9 Hz, 2H), 7.79 (d,³J_(HH)=7.7 Hz, 2H), 6.64 (d, ³J_(HH)=7.7 Hz, 2H), 7.40 (dd, ³J_(HH)=5.2Hz, 2H), 7.12 (dd, ³J_(HH)=5.2 Hz, 2H).

Preparation of 4-bromo-7-(2′-bromo-5′-thienyl)-2,1,3-benzothiadiazole(N2S-1)-T1-Br2

2.1 g (11.38 mmol) of N-bromosuccinimide were added to a solution of2.93 g (9.9 mmol) of 4-bromo-7-(thien-2-yl)-2,1,3-benzothiadiazoline in250 ml of chloroform and 150 ml of ethyl acetate over a period of 15minutes at RT in a protective gas atmosphere and with exclusion oflight. The mixture was stirred for 6 hours, and 50 ml of saturatedNa₂CO₃ solution were subsequently added, the organic phase was separatedoff and dried over Na₂SO₄. After removal of the solvent, the residue wasrecrystallized from DMF/EtOH. Drying at 50° C. under reduced pressuregave the dibromo compound in the form of yellow-orange crystals whichaccording to HPLC had a purity of about 99.6%. The yield was 3.2 g(87%).

¹H NMR (CDCl₃, 500 MHz): [ppm]=8.07 (d, ³J_(HH)=7.7 Hz, 1H), 8.01 (d,³J_(HH)=7.7 Hz, 1H), 7.93 (d, ³J_(HH)=4.0 Hz, 1H), 7.38 (d, ³J_(HH)=4.0Hz, 1H).

The compounds (CH-a to CH-m, 5,6)-T1-Br2 could be prepared analogously.

A6: Preparation of Further Monomers which can be Used in Copolymers:

Preparation of1-(2-ethylhexyloxy)-4-methoxy-2,5-bis(4-bromo-2,5-dimethoxystyryl)benzene(MX-1)

10.5 g (19.5 mmol) of1-(2-ethylhexyloxy)-4-methoxy-2,5-methylenephosphonate were dissolved in85 ml of dry DMF and admixed under nitrogen with 2.4 g (43 mmol) ofNaOMe and subsequently with 10.6 g (43 mmol) of4-bromo-2,5-dimethoxybenzaldehyde. The orange suspension was stirred atRT for 5 hours, poured into water, the yellow precipitate was filteredoff, washed with MeOH and n-hexane and recrystallized twice fromtoluene/hexane. This gave 11.8 g (83%) of the bisphenylenevinylene asyellow needles having a purity of 99.8%, determined by RP-HPLC.

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.43 (m, 4H), 7.18 (s, 1H), 7.17 (s, 1H),7.14 (s, 2H), 7.10 (s, 2H), 3.97 (m, 2H), 3.93 (s, 3H), 3.92 (s, 3H),3.91 (s, 3H), 3.85 (s, 6H), 1.81 (m, 1H), 1.61 (m, 4H), 1.35 (m, 4H),0.98 (t, ³J_(HH)=7.4 Hz, 3H), 0.89 (t, ³J_(HH)=7.3 Hz, 3H).

Preparation of2,3,6,7-tetra-(2-methylbutyloxy)-2′,7′-(4-bromostyryl)-9,9′-spirobifluorene(MX-2)

12.8 g (13.8 mmol) of2,3,6,7-(2-methylbutyloxy)-9,9′-spirobifluorene-2′,7′-methylenephosphonatewere dissolved in 60 ml of dry DMF, and 1.7 g of NaOMe and 5.6 g (30.4mmol) of bromobenzaldehyde in 20 ml of dry DMF were added one after theother. The mixture was heated at 90° C. for 6 hours, subsequently pouredinto water, the precipitate was filtered off with suction, washed withH₂O, MeOH and hexane and recrystallized twice from toluene/hexane. Thisgave the spirobifluorene in the form of yellow platelets having a purityof 99.7%, determined by RP-HPLC.

¹H NMR (CDCl₃, 500 MHz): [ppm]=7.78 (d, ³J_(HH)=7.7 Hz, 2H, spiro), 7.49(dd, ³J_(HH)=8.0 Hz, ⁴J_(HH)=1.4 Hz, 2H, spiro), 7.40 (d, ³J_(HH)=9.0Hz, 4H phenylene), 7.26 (m, 6H, phenylene, spiro), 6.91 (2 d,³J_(HH)=16.1 Hz, 4H, olefin), 6.88 (s, 2H, spiro), 6.2 (s, 2H, spiro),3.95 (m, 4H, CH₂), 3.55 (m, 4H, CH₂), 1.95 (m, 2H, CH₂), 1.75 (m, 2H,CH₂), 1.64 (m, 2H, CH), 1.48 (m, 2H, CH), 1.34 (m, 2H, CH₂), 1.18 (m,2H, CH₂), 1.09 (d, ³J_(HH)=6.7 Hz, 6H, CH₃), 0.99 (t, ³J_(HH)=7.3 Hz,6H, CH₃), 0.93 (d, ³J_(HH)=9.7 Hz, 6H, CH₃), 0.86 (t, ³J_(HH)=7.5 Hz,6H, CH₃).

Preparation of 1,4-dibromo-2,5-(4-fluorostyryl)benzene (MX-3)

15.3 g of 1,4-dibromobenzene-2,5-methylenephosphonate were dissolved in60 ml of DMF, 3.3 g (60 mmol) of NaOMe were added and a solution of 7.1g (57 mmol) in 10 ml of DMF was subsequently added dropwise withevolution of heat. After 10 minutes, the yellow solution was poured intowater and the yellow, felt-like solid was filtered off with suction andwashed with water, MeOH and hexane. The solid was recrystallized threetimes from CHCl₃ to give 10 g (70%) of yellow needles having a purity of99.9% (RP-HPLC).

¹H NMR (d₂-tetrachloroethane 500 MHz): [ppm]=7.85 (s, 2H,dibromophenyl), 7.53 (m, 4H, phenylene), 7.28 (d, ³J_(HH)=16.1 Hz, 2H,olefin), 7.09 (m, 4H, phenylene), 7.04 (d, ³J_(HH)=16.1 Hz, 2H, olefin).

Preparation of 2,7-dibromo-2′,7′-N,N-diphenylamino-9,9′-spirobifluorene(MX-4) (A) 2,7-Diiodo-2′,7′-dibromo-9,9′-spirobifluorene

92.0 g (194.1 mmol) of 2,7-dibromospirobifluorene were dissolved in 200ml of CHCl₃, after which 100.1 g (233 mmol) ofbis(trifluoroacetoxy)iodobenzene and 59.0 g of I₂ were added and themixture was stirred at RT under nitrogen for 12 hours. The suspensionwas filtered, the residue washed with CHCl₃ and recrystallized twicefrom 1,4-dioxane. The yield of the diiodated spirobifluorene was 121.4 g(86%) at a purity of >99% (¹H-NMR).

¹H NMR (DMSO-d₆, 500 MHz)-8.04 (d, ³J_(HH)=7.9 Hz, 2H), 7.88 (d,³J_(HH)=7.9 Hz, 2H), 7.82 (dd, ³J_(HH)=7.9 Hz, ⁴J_(HH)=1.5 Hz, 2H), 7.66(dd, ³J_(HH)=8.3 Hz, ⁴J_(HH)=1.9 Hz, 2H), 6.98 (d, ⁴J_(HH)=1.2 Hz, 2H),6.83 (d, ⁴J_(HH)=1.5 Hz, 2H).

(B) 2,7-Dibromo-2′,7′-N,N-diphenylamino-9,9′-spirobifluorene (MX-4)

30.0 g (41 mmol) of 2,7-diiodo-2′,7′-dibromo-9,9′-spirobifluorene and15.1 g (93 mmol) of diphenylamine were dissolved in toluene and thesolution was saturated with N₂, after which 93 mg (0.41 mmol) ofPd(OAc)₂, 167 mg (0.82 mmol) of tris-o-tolylphosphine and 11 g (115mmol) of NaO^(t)Bu were added in succession and the resulting suspensionwas heated at 70° C. for 12 hours. After this time, 20 ml of 1% strengthNaCN solution were added dropwise, the mixture was stirred for 2 hoursand the solid which precipitated was filtered off with suction. Thesolid was washed with H₂O and EtOH and recrystallized three times withtoluene. This gave 21.7 g (65%) of the diamine in the form of colorlesscrystals having a purity of 99.6% (RP-HPLC).

¹H NMR (DMSO-d₆, 500 MHz): [ppm]=7.83 (m, 4H, spiro), 7.56 (dd,³J_(HH)=8.1 Hz, ⁴J_(HH)=2.0 Hz, 2H, spiro), 7.18 (m, 8H, N-phenyl), 6.96(m, 6H, N-phenyl, spiro), 6.88 (m, 10H, N-phenyl, spiro), 6.19 (d,⁴J_(HH)=2.0 Hz, 2H, spiro).

To give a better overview, the monomers described in A6 are depictedbelow:

Copolymerization of 87.5 mol % of 2,7-dibromo-2′, 3′,6′,7′-tetra(2-methylbutyloxy)-spirobifluorene (S-SY1) and 12.5 mol % ofN,N′-bis(4-bromo)phenyl-N,N′-bis(4-tert-butylphenyl)benzidine (AM1) byYamamoto coupling (polymer P1)

1.53 g (5.57 mmol) of Ni(COD)₂ and 0.87 g (5.57 mmol) of 2,2′-bipyridylwere introduced under argon into a Schlenk vessel. 25 ml ofdimethylformamide and 80 ml of toluene were added and the mixture washeated to 80° C. After 30 minutes, firstly 0.379 g (3.51 mmol, 0.43 ml)of 1,5-cyclooctadiene and then a solution of 1.768 g (2.11 mmol) of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1)and 0.183 g (0.242 mmol) ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)-benzidine (AM1) in20 ml of toluene were added. After 144 hours, the mixture was cooled, 5ml of HCl in dioxane were added and the reaction mixture was stirred for15 minutes. 50 ml of chloroform were added and the mixture was stirredfor 15 minutes. The organic phase washed twice with 100 ml each time of5M HCl and once with 100 ml of saturated NaHCO₃ solution. The solutionwas precipitated in 450 ml of methanol and the crude polymer wasfiltered off with suction. It was reprecipitated twice from 100 ml ofTHF/150 ml of methanol in each case. This gave 1.30 g (2.24 mmol, 83%)of fibrous, light-yellow polymer P1.

¹H NMR (CDCl₃): [ppm]=7.7-6.7 (m, 9.4H, spiro, TAD); 6.2-6.0 (m, 2H,spiro); 4.0-3.2 (2×m, 7.2H, OCH₂); 1.9-0.7 (m, alkyl H, includingt-butyl at 1.30).

GPC: THF; 1 ml/min, Plgel 10 μm Mixed-B 2×300×7.5 mm², 35° C., RIdetection: Mw=155 000 g/mol, Mn=53 000 g/mol

Copolymerization of 50 mol % of the ethylene glycol ester of2′,3′,6′7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 40 mol % of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1)and 10 mol % ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1) bymeans of the Suzuki reaction (polymer P2).

8.0065 g (10.00 mmol) of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 6.5499 g (8.00 mmol) of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1),1.5173 g (2.00 mmol) ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1),9.67 g (42 mmol) of K₃PO₄·H₂O, 30 ml of toluene, 15 ml of water and 0.25ml of ethanol were degassed for 30 minutes by passing N₂ through themixture. 175 mg (0.15 mmol) of Pd(PPh₃)₄ were subsequently added underprotective gas. The suspension was stirred vigorously under a blanket ofN₂ at an internal temperature of 87° C. (gentle reflux). After 4 days, afurther 0.30 g of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acidwas added. After heating for a further 6 hours, 0.3 ml of bromobenzenewas added and the mixture was refluxed for another 3 hours.

The reaction solution was diluted with 200 ml of toluene and was thenstirred with 200 ml of 2% strength aqueous NaCN solution for 3 hours.The mixture became virtually colorless during this time. The organicphase washed with H₂O and precipitated by dropwise addition to 800 ml ofethanol. The polymer was dissolved in 200 ml of THF at 40° C. over aperiod of 1 hour, precipitated with 250 ml of MeOH, washed and driedunder reduced pressure. The solid was reprecipitated once more in 200 mlof THF/250 ml of methanol, filtered off with suction and dried toconstant mass. This gave 12.25 g (18.8 mmol, 94%) of the polymer P2 as alight-yellow solid.

¹H NMR (CDCl₃): [ppm]=7.7-6.7 (m, 9.4H, spiro, TAD); 6.2-6.0 (m, 2H,spiro); 4.0-3.2 (2×m, 7.2H, OCH₂); 1.9-0.7 (m, alkyl H, includingt-butyl at 1.30).

GPC: THF; 1 ml/min, PLgel 10 μm Mixed-B 2×300×7.5 mm², 35° C., RIdetection: Mw=124 000 g/mol, Mn=39 000 g/mol.

Example P3 copolymerization of 50 mol % of the ethylene glycol ester of2′,3′, 6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 30 mol % of 2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1), 10 mol % of5,8-dibromodiphenylquinoxaline (CH-b) and 10 mol % ofN,N-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1) bymeans of the Suzuki reaction (polymer P13).

4.9124 g (6.00 mmol) of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 8.0065 g (10.00 mmol) of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1),0.8803 g (2.00) of 5,8-dibromodiphenylquinoxaline (CH-b), 1.5173 g (2.00mmol) of N,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine(AM1), 9.67 g (42 mmol) of K₃PO₄·H₂O, 30 ml of toluene, 15 ml of waterand 0.25 ml of ethanol were degassed for 30 minutes by passing N₂through the mixture. 175 mg (0.15 mmol) of Pd(PPh₃)₄ were subsequentlyadded under protective gas. The suspension was stirred vigorously undera blanket of N₂ at an internal temperature of 87° C. (gentle reflux).After 4 days, a further 0.30 g of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acidwas added. After heating for a further 6 hours, 0.3 ml of bromobenzenewas added and the mixture was refluxed for another 3 hours.

The reaction solution was diluted with 200 ml of toluene and stirredwith 200 ml of 2% strength aqueous NaCN solution for 3 hours. Themixture became virtually colorless during this time. The organic phasewashed with H₂O and precipitated by adding it dropwise to 800 ml ofethanol. The polymer was dissolved in 200 ml of THF at 40° C. over aperiod of 1 hour, precipitated with 250 ml of MeOH, washed and driedunder reduced pressure. The solid was reprecipitated once more in 200 mlof THF/250 ml of methanol, filtered off with suction and dried toconstant mass. This gave 17.8 g (18.6 mmol, 93%) of the polymer P13 as alight-yellow solid.

¹H NMR (CDCl₃): [ppm]=7.8-6.7 (m, 9.6H, spiro, TAD); 6.4-6.0 (m, 2H,spiro); 4.0-3.4 (2×m, 6.4H, OCH₂); 1.9-0.7 (m, alkyl H, includingt-butyl at 1.30).

GPC: THF; 1 ml/min, PLgel 10 μm Mixed-B 2×300×7.5 mm², 35° C., RIdetection: Mw=54 000 g/mol, Mn=22 000 g/mol.

Example P4 Copolymerization of 50 mol % of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 30 mol % of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1),10 mol % ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1) and10 mol % of2,3,6,7-tetra(2-methylbutyloxy)-2′,7′-(4-bromostyryl)-9,9′-spirobifluorene(MX-2) by means of the Suzuki reaction (improved version) (polymerP35*).

Polymerization Method as Described in the Unpublished Patent ApplicationDE 10159946.3:

16.0131 g (20.00 mmol) of the ethylene glycol ester of2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene-2,7-bisboronic acid(S-SY2), 9.8249 g (12.00 mmol) of2,7-dibromo-2′,3′,6′,7′-tetra(2-methylbutyloxy)spirobifluorene (S-SY1),3.0346 g (4.00 mmol) ofN,N′-bis(4-bromophenyl)-N,N′-bis(4-tert-butylphenyl)benzidine (AM1),4.0923 g (4.00 mmol) of2,3,6,7-tetra(2-methylbutyloxy)-2′,7′-(4-bromostyryl)-9,9′-spirobifluorene(MX-2), 19.57 g (85 mmol) of K₃PO₄·H₂O, 250 ml of toluene, 250 ml ofdioxane, 40 ml of water were degassed for 30 minutes by passing argonthrough the mixture. A mixture of 2.25 mg (0.01 mmol) of PdAc₂ and 18.3mg (0.06 mmol) of P(o-tolyl)₃ in 1 ml of toluene was subsequently addedunder protective gas. The suspension was stirred vigorously under ablanket of argon for about 5 hours under gentle reflux. During thistime, the reaction mixture became viscous and displayed a bluishfluorescence. 118 mg (0.4 mmol) of3,4-bis(2-methylbutyloxy)benzeneboronic acid in 150 ml of toluene weresubsequently added and the mixture was refluxed for another one hour.Finally, 165 mg (0.5 mmol) of 3,4-bis(2-methylbutyloxy)bromobenzene in afurther 100 ml were added and the mixture was refluxed for another onehour.

The reaction mixture was cooled, the aqueous phase was separated off andwas subsequently stirred twice with 250 ml each time of a 5% strengthsodium diethyldithiocarbamate solution in water at 60° C. It wassubsequently stirred three times with 250 ml each time of water, dilutedwith 750 ml of THF and the crude polymer was finally precipitated byaddition of 2 l of methanol. This was purified further by beingreprecipitated twice from THF (1% strength solution) in methanol. Finalpurification was carried out by Soxhlet extraction with methanol/THF(1:1) for about 48 hours.

24.14 g (90%) of polymer were obtained as yellow fibers.

¹H NMR (CDCl₃): 7.8-6.2 (m, 12.6H, spiro, vinyl, TAD); 4.0-3.3 (2×m,7.2H, OCH₂); 1.9-0.7 (m, 34.2H, alkyl H, including t-butyl at 1.25).GPC: THF; 1 ml/min, PLgel 10 μm Mixed-B 2×300×7.5 mm², 35° C., RIdetection: Mw=830 000 g/mol, Mn=220 000 g/mol.

This polymer had a higher molecular weight than the polymer P35 listedin the table (see below), which had been prepared by the oldpolymerization method.

This also enabled a few property changes to be achieved; some furtherdata:

-   -   Viscosity data: solution (P35*) in anisole/o-xylene (14 g/l):        20.8 mPas (@ 40 s⁻¹); solution (P35*) in tetralin (8 g/l): 15.8        mPas (@ 40 s⁻¹).    -   EL data: max. eff.: 5.35 Cd/A; 3.8 V@ 100 Cd/m²; color: light        blue (CIE-1931: x/y=0.18, 0.25); operating life (@100 Cd/m²):        4000 h.

Further polymers were prepared by methods analogous to those describedfor P1, P2 and P13. The chemical properties are summarized in thefollowing table. All these polymers were also examined for use in PLEDs.The way in which PLEDs can be produced has been indicated above and isdescribed in more detail in part C. The most important device properties(color, efficiency and life) are also listed in the table.

Electroluminescence*** GPC** Voltage Life at Proportion of the monomersM_(W) M_(N) Max. at 100 100 Visco.**** Polymer in the polymerization [%](1000 (1000 λ_(max) eff Cd/m² EL Cd/m² Gel temp. (Type)* Monom. 1 Monom.2 Monom. 3 Monom. 4 g/mol) g/mol) [nm] [Cd/A] [V] color [h] [° C.] P1(Y) 87.5% S-SY1 12.5% AM1 155 53 465 2.7 4.0 blue 800 <0° C. P2 (S) 50%S-SY2 40% S-SY1 10% AM1 124 39 463 2.8 4.5 blue 1250 <0° C. P3 (S) 50%S-SY2 40% S-US1 10% AM1 101 41 465 2.6 4.5 blue 1150 <0° C. P4 (S) 50%S-SY2 40% S-US2 10% AM1 90 40 470 3.0 4.7 blue 1550 10° C. P5 (S) 50%S-SY2 40% S-US3 10% AM1 115 45 473 3.2 4.2 blue 2250 <0° C. P6 (S) 50%S-SY2 40% S-US4 10% AM1 87 36 472 2.8 4.5 blue 1250 <0° C. P7 (S) 50%S-SY2 40% S-SY3 10% AM1 120 46 467 1.9 5.1 blue 610 10° C. P8 (S) 50%S-SY4 40% S-SY1 10% AM1 110 38 468 1.8 5.3 blue 410 15° C. P9 (S) 50%S-SY2 40% S-SY1 10% AM2 89 30 470 2.2 5.0 blue 900 <0° C. P10 (S) 50%S-SY2 40% S-SY1 10% AM3 83 29 465 1.6 5.6 blue 800 <0° C. P11 (S) 50%S-SY2 40% S-SY1 10% AM1 124 39 463 2.8 4.5 blue 1250 <0° C. P12 (S) 50%S-SY2 30% S-SY1 10% AM1 10% CH-a 98 48 509 6.8 5.8 green 3000 <0° C. P13(S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-b 77 32 516 7.6 4.6 green 4300<0° C. P14 (S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-c 99 29 516 5.9 5.8green 2800 <0° C. P15 (S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-d 110 51545 6.9 4.7 green- 4000 <0° C. yellow P16 (S) 50% S-SY2 30% S-SY1 10%AM1 10% CH-e 105 37 527 7.7 3.9 green >5000 <0° C. P17 (S) 50% S-SY2 30%S-SY1 10% AM1 10% CH-f 120 48 525 6.0 4.9 green 2100 <0° C. P18 (S) 50%S-SY2 30% S-SY1 10% AM1 10% CH-g 29 10 525 3.1 7.1# green — ~20° C.  P19(S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-h 91 29 535 6.7 3.8 green >5000<0° C. P20 (S) 50% S-SY2 30% S-SY1 20% CH-h 87 36 534 6.1 4.1 green 4000<0° C. P21 (S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-i 124 63 553 6.5 4.8green- 2500 <0° C. yellow P22 (S) 50% S-SY2 30% S-SY1 10% AM1 10% CH-k54 20 541 2.2 5.8 green- — ~5° C. yellow P23 (S) 50% S-SY2 30% S-SY1 10%AM1 10% CH-l 111 54 524 5.9 5.1 green 1800 <0° C. P24 (S) 50% S-SY2 20%S-SY1 20% MX-4 10% CH-b 138 56 516 8.8 3.8 green >5000 <0° C. P25 (S)50% S-SY2 30% S-SY1 10% AM1 10% N2S-1 98 37 551 7.1 4.9 green- 1600 <0°C. yellow P26 (S) 50% S-SY2 30% S-SY1 10% AM1 10% N2O-1 87 39 575 6.25.4 yellow 1200 <0° C. P27 (S) 50% S-SY2 10% AM1 35% N2S-1 5%(N2S- 89 40632 1.5 3.6 red >5000 <0° C. 1)-T2-Br2 P28 (S) 50% S-SY2 10% AM1 35%N2S-1 5%(N2S- 112 45 597 1.6 4.9 red- >5000 <0° C. 1)-T1-Br2 orangeP29(S) 50% S-SY2 10% AM1 35% N2S-1 5%(CH-b)- 56 20 619 1.5 3.5 red >5000<0° C. T2-Br2 P30(S) 50% S-SY2 10% AM1 35% N2S-1 5%(CH-b)- 89 45 590 1.93.9 red- >5000 <0° C. T1-Br2 orange P31(S) 50% S-SY2 10% AM1 35% N2S-15%(5)-T2- 120 62 560 3.2 4.9 yellow- — <0° C. Br2 orange P32(S) 50%S-SY2 10% AM1 35% N2S-1 5%(6)-T2- 79 30 575 1.0 6.9 yellow- — <0° C. Br2orange P33(S) 50% S-SY2 10% MX-1 35% N2S-1 5%(N2S- 117 48 642 1.9 3.0red >5000 <0° C. 1)-T2-Br2 P34 (S) 50% S-SY2 30% S-SY1 10% AM1 10% MX-1135 53 520 9.8 3.5 green >5000 <0° C. P35 (S) 50% S-SY2 30% S-SY1 10%AM1 10% MX-2 102 45 475 4.0 4.2 blue- 2100 <0° C. green P36 (S) 50%S-SY2 30% S-SY1 10% AM1 10% MX-3 65 25 460 2.0 4.4 blue 1200 <0° C. P37(S) 50% S-SY2 30% S-SY1 10% AM1 10% MX-4 128 60 468 3.2 4.0 blue 2000<0° C. P38 (S) 50% S-SY2 20% S-SY1 10% AM1 20% MX-4 99 39 468 3.2 3.8blue 1900 <0° C. P39 (Y) 80% S-SY1 10% AM1 10% MX-4 176 76 466 3.3 4.0blue 2500 <0° C. P40 (S) 50% S-SY2 20% S-SY1 10% AM1 10% MX-4 112 60 51710.2 3.0 green >5000 <0° C. 10% CH-b P41 (S) 50% S-SY2 20% S-SY1 10% AM110% MX-1 122 62 515 11.2 2.9 green >5000 <0° C. 10% CH-b V1 (S) 50%S-SY2 50% S-SY1 142 62 451 0.1 8.9 blue — <0° C. V2 (S) 50% S-SY2 40%S-SY1 10% MX-1 102 60 518 2.1 9.3 green 100 h <0° C. V3 (S) 50% S-SY225% S-SY1 25% MX-1 99 38 523 2.0 9.2 green  80 h <0° C. *S = Prepared bySuzuki polymerization (cf. Ex. P2), Y = prepared by Yamamotopolymerization (cf. Ex. P1) **GPC measurements in THF; 1 ml/min, Plgel10 μm Mixed-B 2 × 300 × 7.5 mm², 35° C., RI detection was calibratedagainst polystyrene ***For preparation of the polymeric LEDs, see part C****Solutions of the polymer (10 mg/ml) in toluene were heated to 60°C., cooled at 1° C./minute and the viscosity was measured on aBrookfield LVDV-III rheometer (CP-41). At the gel temperature determinedin this way, a sharp increase in the viscosity occurred. #Owing to thepoor solubilily, the PLEDs were produced from chlorobenzene.

Part C: Production and Characterization of LEDs:

LEDs were produced by the general method outlined below. This naturallyhad to be adapted in each individual case to the particularcircumstances (e.g. polymer viscosity and optimal layer thickness of thepolymer in the device). The LEDs described below were in each casetwo-layer systems, i.e. substrate//ITO//PEDOT//polymer//cathode. PEDOTis a polythiophene derivative which can, for example, be procured fromBAYER AG as Baytron P™

General Method of Producing Highly Efficient, Long-Life. LEDs:

After the ITO-coated substrates (e.g. glass support, PET film) have beencut to the correct size, they are cleaned in a number of cleaning stepsin an ultrasonic bath (e.g. soap solution, Millipore water,isopropanol).

They are dried by blowing with an N₂ gun and stored in a desiccator.Before coating with the polymer, they are treated in an ozone plasmaapparatus for about 20 minutes. A solution of the respective polymer(generally with a concentration of 4-25 mg/ml in, for example, toluene,chlorobenzene, xylene:cyclohexanone (4:1)) is made up and dissolved bystirring at room temperature. Depending on the polymer, it can also beadvantageous to stir at 50-70° C. for some time. When the polymer hasdissolved completely, the solution is filtered through a 5 μm filter andapplied by means of a spin coater at varying speeds (400-6000). Thelayer thicknesses can in this way be varied in a range from about 50 to300 nm. The measurements are carried out using a Dektak instrument asdescribed in EP 1029019. A conductive polymer, preferably doped PEDOT orPANI, is usually applied to the (structured) ITO beforehand.

Electrodes are then applied to the polymer films. This is generallycarried out by thermal vapor deposition (Balzer BA360 or Pfeiffer PL S500). The transparent ITO electrode is then connected as anode and themetal electrode (e.g. Ba, Yb, Ca) is connected as cathode and the deviceparameters are determined.

The results obtained using the polymers described are summarized in thetable in part B.

1. A monomer having the formula (I)

wherein X is, identically or differently on each occurrence, CH, CR¹, orN; Z is, identically or differently on each occurrence, a singlechemical bond, a CR³R⁴ group, a —CR³R⁴—CR³R⁴— group, a —CR³═CR⁴— group,O, S, N—R⁵, C═O, C═CR³R⁴ or SiR³R⁴; R¹ is, identically or differently oneach occurrence, N(R⁵)₂ or N(R⁵)₃ ⁺; R² is, identically or differentlyon each occurrence, a linear, branched, or cyclic alkyl or alkoxy chainhaving up to 22 carbon atoms wherein one or more nonadjacent carbonatoms is optionally replaced by N—R⁵, O, S, —CO—O—, or O—CO—O, andwherein one or more H atoms is optionally replaced by fluorine; or is anaryl or aryloxy group having from 5 to 40 carbon atoms and is optionallysubstituted by one or more nonaromatic radicals R¹, wherein one or morecarbon atoms is optionally replaced by O, S, or N which is; or is CN; R³and R⁴ are, identically or differently on each occurrence, is H; alinear, branched, or cyclic alkyl chain having up to 22 carbon atomswherein one or more nonadjacent carbon atoms is optionally replaced byN—R⁵, O, S, —CO—O—, or O—CO—O, and wherein one or more H atoms isoptionally replaced by fluorine, or are each an aryl group having from 5to 40 carbon atoms and is optionally substituted by one or morenonaromatic radicals R¹, wherein one or more carbon atoms is optionallyreplaced by O, S, or N; or are each CN; and wherein a plurality of R³and/or R⁴ optionally define a ring; R⁵ is, identically or differently oneach occurrence, H; a linear, branched, or cyclic alkyl chain having upto 22 carbon atoms wherein one or more nonadjacent carbon atomsoptionally replaced by O, S, —CO—O—, or O—CO—O, and wherein one or moreH atoms is optionally replaced by fluorine; or is an aryl group havingfrom 5 to 40 carbon atoms optionally substituted by one or morenonaromatic radicals R¹, wherein or more carbon atoms is optionallyreplaced by O, S, or N; m is, identically or differently on eachoccurrence, 0, 1, 2, or 3; n is, identically or differently on eachoccurrence, 0, 1, 2, 3, or 4; and Y is, identically or differently oneach occurence, bromine and/or boronic acid ester.
 2. The monomer ofclaim 1, wherein R⁵ is an aryl group having 5 to 40 carbon atomsoptionally substituted by one or more nonaromatic radicals R¹, whereinone or more carbon atoms is optionally replaced by O, S, or N.
 3. Themonomer of claim 1, wherein R⁵ is a phenyl group.
 4. The monomer ofclaim 1, wherein m is
 0. 5. The monomer of claim 1, wherein n is 1 or 2.6. The monomer of claim 1, wherein X is CH.
 7. The monomer of claim 1,wherein Z is a single bond.